CN101300068B - Vanadium/titania catalyst comprising natural manganese ore for removing nitrogen oxides and dioxin in wide operating temperature range and method of using the same - Google Patents

Vanadium/titania catalyst comprising natural manganese ore for removing nitrogen oxides and dioxin in wide operating temperature range and method of using the same Download PDF

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CN101300068B
CN101300068B CN2006800412255A CN200680041225A CN101300068B CN 101300068 B CN101300068 B CN 101300068B CN 2006800412255 A CN2006800412255 A CN 2006800412255A CN 200680041225 A CN200680041225 A CN 200680041225A CN 101300068 B CN101300068 B CN 101300068B
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catalyst
vanadium
dioxin
nmo
nitrogen oxide
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CN101300068A (en
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洪性镐
李俊烨
洪锡舟
赵成必
洪性昌
李镀坰
崔相炫
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KOREA POWER ENGINEERING Co Inc
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
    • B01D53/565—Nitrogen oxides by treating the gases with solids
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    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/72—Organic compounds not provided for in groups B01D53/48 - B01D53/70, e.g. hydrocarbons
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/20—Vanadium, niobium or tantalum
    • B01J23/22—Vanadium
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    • B01D2255/00—Catalysts
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    • B01D2255/207—Transition metals
    • B01D2255/20707—Titanium
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    • B01D2255/20723—Vanadium
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    • B01D2255/2073—Manganese
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    • B01D2255/20776—Tungsten
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/20—Halogens or halogen compounds
    • B01D2257/206—Organic halogen compounds
    • B01D2257/2064—Chlorine
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0036—Grinding

Abstract

Disclosed is a vanadium/titania-based catalyst including natural manganese ore for removing nitrogen oxides and dioxin in a wide operating temperature range and a method of using the same. Specifically, this invention pertains to a vanadium/titania (V/TiO2)-based catalyst including natural manganese ore for removing nitrogen oxides and dioxin in a wide operating temperature range, in which the WTiO2 catalyst for selective catalytic reduction of nitrogen oxides and removal of dioxin contained in flue gas includes 5-30 wt% of natural manganese ore, thus exhibiting excellent activity of removingnitrogen oxides even in the low temperature range and of removing dioxin at the same time, and to a method of using the same. The catalyst of this invention has good thermal stability and thus can simultaneously manifest nitrogen oxides removal performance and dioxin removal performance superior to conventional vanadium/titania catalysts in a wide temperature range (150 to 450 DEG C) including not only a high temperature range but also a low temperature range. As well, since unreacted ammonia emissions can be reduced, the formation of an ammonium salt is prevented and ammonium nitrate is decomposed at low temperatures, thus solving the problems of inactivation of the catalyst due to catalytic poisoning and of a shortened lifetime thereof, leading to economic benefits.

Description

The method that is used in wide operating temperature range, removing the vanadium/titania catalyst that comprises natural manganese ore of nitrogen oxide and dioxin and uses this catalyst
[technical field]
The present invention relates to be used in wide operating temperature range, removing the vanadium/titania base (V/TiO that comprises natural manganese ore (NMO) of nitrogen oxide and dioxin 2) catalyst, and the method for using this catalyst.More specifically, the present invention relates to be used in wide operating temperature range, removing the V/TiO that comprises NMO of nitrogen oxide and dioxin 2Catalyst, wherein V/TiO 2Catalyst mixes with NMO, improving the activity remove nitrogen oxide in temperature range, thereby not only just at high temperature and under low temperature also can remove nitrogen oxide and dioxin effectively, and relate to the method for using this catalyst.
[background technology]
Usually, combustion of fossil fuel produce be used for steam power plant and industrial synthesis energy, and in incinerator burning with the volume that reduces discarded object with improve its chemical stability.In these situations, produce various harmful exhausts, for example carbon dioxide, sulfur dioxide (SO 2), nitrogen oxide (NO x), dioxin, VOC, heavy metal etc.In these waste gas, nitrogen oxide is environmental contaminants, and is harmful, and produces photochemical smog or shorten visibility distance.Nitrogen oxide is mainly by nitric oxide (NO) and nitrogen dioxide (NO 2) form, wherein NO accounts for 95% of whole nitrogen oxide.Like this, form production process according to it, nitrogen oxide is divided into hot NO x, promote (prompt) NO xWith fuel NO x
In the situation of the burning boiler that uses fossil fuel, fuel is carried out preliminary treatment, perhaps improve fuel condition to reduce the discharging of nitrogen oxide.But, from considering aspect economy and the efficient that the burning post-processing approach that needs additional process steps after burning is effective.This class burning post processing comprises catalytic cracking, SCR (SCR), SNCR (SNCR), non-selective catalytic reduction (NSCR) and plasma treatment.At present, the SCR that uses the ammonia reducing agent to carry out is the most effective.
By SCR, on the surface of denitrification catalyst, shown in reaction 1-5, react based on ammonia:
Reaction 1
4NO+4NH 3+O 2→4N 2+6H 2O
Reaction 2
2NO 2+4NH 3+O 2→3N 2+6H 2O
Reaction 3
6NO+4NH 3→5N 2+6H 2O
Reaction 4
6NO 2+8NH 3→7N 2+12H 2O
Reaction 5
NO+NO 2+2NH 3→2N 2+3H 2O
Although can be used for can making by the whole bag of tricks based on the denitrification catalyst of the SCR of ammonia, the denitrification catalyst that comprises titania support, vanadium and optional tungsten at present shows the highest efficient, and therefore industrialization is used in worldwide.V/TiO 2Catalyst has high activity at 300-400 ℃ usually, but removes decrease in efficiency in the temperature that is lower than said temperature owing to low-activation energy causes nitrogen oxide.On the other hand, be higher than the temperature of said temperature, the ammonia reducing agent is oxidized, and the result makes the stoichiometric proportion of reaction improper, has reduced efficient unfriendly.In addition, the heat fatigue of catalyst increases, and causes life of catalyst to shorten.
In waste gas, there are water and oxysulfide usually.These materials can generate ammonium salt on denitrification catalyst, reduce activity of such catalysts.The reaction of catalyst poisoning is carried out according to following reaction 6-8:
Reaction 6
2SO 2+O 2→2SO 3
Reaction 7
NH 3+SO 3+H 2O→NH 4HSO 4
Reaction 8
SO 3+H 2O→H 2SO 4
The sulfur trioxide that generates in the reaction 6 forms sulfate in reaction 7, sulfate can remain on the catalyst surface not decomposing on the catalyst surface, thereby makes catalyst poisoning.In addition, the sulfuric acid that generates in the reaction 8 can corrode the equipment in catalyst bed and the system's follow-up phase.
Because generating sulfur trioxide according to reaction 6 at high temperature carries out energetically, therefore need exploitation can under low temperature, realize the catalyst of splendid nitrogen oxide SCR, generate farthest to reduce above-mentioned substance, thereby reduce the formation of sulfate and sulfuric acid in reaction 7 and the reaction 8.
In addition, make SCR at low temperatures another major reason of inactivation be to form down ammonium nitrate by the low temperature that being reflected at of following reaction 9 and 10 expressions is equal to or less than 200 ℃:
Reaction 9
2NH 3+2NO 2→NH 4NO 3+N 2+H 2O
Reaction 10
2NH 3+H 2O+2NO 2→NH 4NO 3+NH 4NO 2
Ammonium nilrite (the NH that generates in the reaction 9 4NO 2) be very unsettled, therefore,, can not bring too big problem being equal to or higher than under 60 ℃ the temperature and can decomposing.But, the ammonium nitrate (NH that generates in the reaction 10 4NO 3) must consider, because the fusing point of this material is 170 ℃.Below reaction 11-13 has shown the decomposition of solid ammonium nitrate:
Reaction 11
NH 4NO 3(S)→NH 3+HNO 3
Reaction 12
NH 4NO 3(S)→N 2O+2H 2O
Reaction 13
2NH 4NO 3(S)→2N 2+O 2+4H 2O
Usually, at V/TiO 2There is effective SCR down in catalyst, because the temperature of waste gas should remain in 300-400 ℃ the high temperature range, can support that the method for SCR is restricted on waste gas processing method.For example, in the situation of the steam power plant that uses coal or oil, the temperature behind the fuel economizer of boiler can be about 350 ℃ high temperature, therefore the SCR system can be installed.But because dust and/or sulfur dioxide with high concentration, the avtive spot of denitrification catalyst reduces, and denitrification catalyst also may wear and tear.In addition, because sulfur trioxide (SO 3) oxidation, in the equipment of system's follow-up phase, may form ammonium sulfate, cause these equipment corrosions.Therefore, proposed the SCR system is installed in the method in the downstream of dust arrester and desulphurization system.But, because the temperature of waste gas obviously descends in by the process of dust arrester and desulphurization system at waste gas, even be necessary to use the denitrification catalyst that under low like this temperature, also is applicable to SCR.Especially in the system that is used for wet exhuast gas desulfurization (WFGD), SCR can not take place in expection, because the temperature of waste gas drops to 100 ℃ or lower, therefore needs extra reheat system.For the actual temperature with waste gas improves about 100 ℃, having known needs to consume big energy, is equivalent to about 5-10% of the whole power capacities of generating equipment.This shows, use commercially available conventional V/TiO 2The nitrogen emission of catalyst is the method that consumes big energy, and the energy that is consumed depends on the high temperature active of denitrification catalyst.And, obtain the efficient of being scheduled at low temperatures in order to use high temperature catalyst, should use catalyst in a large number.That is to say that when the amount of catalyst increased, not only catalyst cost, and the cost relevant with the reducing agent supply with the amount of hydrogen-catalyst reactor, pipeline, reducing agent all increased, and the rising of the pressure loss of waste gas, whole system is caused adverse influence.
High-temperature operation has promoted the heat fatigue of catalyst bed, and the result shortens life of catalyst unfriendly.In addition, because sulfur dioxide is highly oxidized, so form ammonium sulfate at the equipment of the follow-up phase of the system that is used for SCR, ammonium sulfate is one of reason for corrosion.In addition, even except ammonium sulfate, also on the surface of denitrification catalyst, form ammonium nitrate, still need and to be lower than the denitrification catalyst that decomposes this class material under the temperature of conventional temperature by catalytic cracking reaction.These performances depend on the good oxidation and/or the reduction of denitrification catalyst.That is to say, in order to solve with economic benefit, to suppress catalysis poisoning material and prolong the relevant problem of catalyst life, with the conventional W/TiO of use 2Difference during catalyst is even need the low-temperature denitrification catalyst that still has higher nitrogen removal performance under 250 ℃ the low temperature being equal to or less than.
Simultaneously, the Mn oxide of NMO causes oxidation and reduction circulation easily, and the oxidation state of the manganese ion of this Mn oxide changes easily, so NMO can be used in the various fields for example denitrogenation, ammoxidation, VOC removal, CO oxidation etc.In addition, known that Mn oxide has very high activity when oxidation, understanding this activity easily is because the change of Mn oxide oxidation state in the gas-solid reaction.In recent years, existing report loads on the pure MnO on the aluminium oxide 2In the SCR reaction of using ammonia to carry out in as reducing agent, temperature range, show very high activity (L.Singoredjo with manganese oxide at 380-570K, R.Kover, F.Kapteijn and J.Moulijn, Applied Catalysis B:Environ., 1,297 (1992)).
About remove nitrogen oxide conventional NMO technology, korean patent application discloses to have disclosed for 1998-086887 number and uses NMO to remove nitrogen oxide under 130-250 ℃ low temperature, and reduces unreacted emission intensity thing by oxidation reaction.Disclose 2002-0051885 number according to korean patent application, at 300-400 ℃ of heat treatment NMO, perhaps make the NMO load be selected from a kind of, two or more metal oxides in tungsten (W), iron (Fe), copper (Cu), vanadium (V), zirconium (Zr), silver (Ag), cerium (Ce), platinum (Pt) and the palladium (Pd), heat-treat at 300-400 ℃ then, to remove nitrogen oxide.In addition, disclose 2000-0031268 number, use the continuous fluid bed bioreactor at NMO (pyrolusite, β-MnO according to korean patent application 2) can remove oxysulfide and nitrogen oxide simultaneously under existing.In addition, according to No. the 732082nd, U.S. Patent application, in order to obtain V/TiO 2The low temperature active of catalyst is a benchmark in the weight of the vanadium of load, V + 4And V + 3Summation (be expressed as V + x(x≤4)) should be equal to or greater than 34 atoms/centimetre 3Weight %, and Ti + 3And Ti + 2Summation (be expressed as Ti + y(y≤3)) should be equal to or greater than 415 atoms/centimetre 3Weight %.
Emission source (for example burning facility) also discharges a large amount of dioxins except the discharging nitrogen oxide, dioxin is the strongest material of toxicity in the known substances so far, and its toxicity is higher 10,000 times than potassium cyanide.In addition, dioxin is non-biodegradable (nobiodegradable), even in the time of 700 ℃, also be stable, accumulation in vivo, human body is caused adverse influence, cause side effect too numerous to enumerate, comprise cancer, genotoxicity, deformity, hepatotoxicity wind agitation, thyroid disease, heart disease etc.
Therefore, in order to reduce the discharging of this dioxin, exemplified before burning, in the burning process and the control method after burning, control method before burning comprises removes the dioxin precursor in advance and discarded object is provided equably, control method in the burning process comprises the suitable operational temperature and the time of staying, combustion air and mixing, farthest reduce fly ash granule, the temperature of control waste gas, the control method after the burning comprises the combination of wet washing device, dry cleaning device, activated carbon sprayer, dust arrester, SNCR and SCR device.In the control method before burning, analyze the composition of discarded object, the relation of the harmful substance that produces after studying it and burning, in advance the discarded object as major pollutants is classified, the amount and the size that join the discarded object in the incinerator are remained unchanged, composition, calorific value, water content and volatile component content are remained unchanged, thereby keep the burning situation in the incinerator equably.
Control method in burning process is controlled following three parameters, that is:
1) temperature is equal to or higher than 850 ℃,
2) time is equal to or greater than 2 seconds,
3) because the geometrical construction of incinerator and the injection of additional air cause turbulent flow.
That is to say that these burning conditions can be controlled effectively and be kept, so unburned carbon or hydrocarbon in the burning gases, particularly can be converted into the precursor of dioxin easily, for example chlorobenzene or polychlorinated biphenyls, volume production that can be less is given birth to.
In the control method after burning, use the active carbon adsorption pollutant, making it then continuously is the most effective by the oxidation catalyst bed with the method for controlling pollutant.But because the problem of technology and catalyst bed aspect of performance, the control of dioxin mainly depends on the suction-operated of using adsorbent, and described adsorbent is activated carbon and calcium hydroxide for example.And the regeneration or the disposal of having adsorbed the adsorbent of dioxin are difficult technically, therefore increase financial burden.That is to say that the method for the dioxin in the present obtainable use active carbon adsorption waste gas has shortcoming, be difficult to regeneration or disposal, therefore economic benefit is caused adverse effect because adsorbed the activated carbon of dioxin.
Usually, by to V 2O 5/ TiO 2The middle WO that adds 3Or MoO 3Catalyst that obtains such as SCR catalyst can be used as the catalyst of oxidation with the dioxin of volatility halogenated organic matters matter form, but its consumption must consider that optimum activity changes.The same with nitrogen oxide, dioxin must be removed under alap temperature.This is because needing less energy heating flame waste gas is favourable economically, and in the presence of metal (Cu, Fe etc.) oxide, is being equal to or higher than under 205 ℃, and the material of catalyst decomposes might synthesize again, and this is disadvantageous.
[summary of the invention]
Technical problem
The inventor is in order to overcome the problem that runs in the prior art, to using the ammonia reducing agent can not only to carry out deeply and thorough research being equal to or less than the method that under 300-400 ℃ high temperature, effectively to remove dioxin and nitrogen oxide under 250 ℃ the low temperature, found that and the NMO of scheduled volume can be joined V/TiO by SCR 2Form the NEW TYPE OF COMPOSITE oxide in the catalyst, this oxide not only at high temperature but also at low temperatures also shows splendid nitrogen removal performance, and can remove dioxin, thereby obtains the present invention.
Therefore, the purpose of this invention is to provide a kind of vanadium/titania catalyst that comprises NMO that is used for removing nitrogen oxide and dioxin in wide operating temperature range, these catalyst not only at high temperature but also under low temperature also can show splendid activity to removing nitrogen oxide and dioxin.
Another object of the present invention provides a kind of method that nitrogen oxide carries out SCR and dioxin removal in wide temperature range.
Technical solution
To achieve these goals, the invention provides a kind of V/TiO that comprises NMO that is used in wide operating temperature range, removing nitrogen oxide and dioxin 2Catalyst is applicable to that wherein the nitrogen oxide that contains in the waste gas carries out SCR and the V/TiO that removes the dioxin that contains in the waste gas 2Catalyst comprises the NMO of 5-30 weight %.
In addition, the invention provides the method that the nitrogen oxide that contains in a kind of waste gas carries out SCR and removes the dioxin that contains in the waste gas, this method is that 150-450 ℃, gas hourly space velocity (GHSV) are 1000-60000 hour in temperature -1And exist under the condition of above-mentioned catalyst and carry out.
[description of drawings]
Fig. 1 shows to be used to estimate the schematic diagram of catalyst of the present invention for the structure of the device of the performance of nitrogen oxide SCR and dioxin removal.
Fig. 2 shows the catalyst (NMO+V/TiO of not tungstenic of the present invention 2(N)), NMO and V/TiO 2(N) nitrogen oxide of catalyst is removed the variation of performance with reaction temperature;
Fig. 3 is presented at and removes nitrogen oxide, the catalyst (NMO+V/TiO of not tungstenic of the present invention 2(N)), NMO and V/TiO 2(N) discharging of the unreacted ammonia of catalyst changes with reaction temperature;
Fig. 4 shows the catalyst (NMO+V/TiO of tungstenic of the present invention 2(W)), NMO and V/TiO 2(W) nitrogen oxide of catalyst is removed the variation of performance with reaction temperature;
Fig. 5 is presented at when removing nitrogen oxide, the catalyst (NMO+V/TiO of tungstenic of the present invention 2(W)), NMO and V/TiO 2(W) discharging of the unreacted ammonia of catalyst is with the variation of reaction temperature;
Fig. 6 shows NMO+V/TiO 2Catalyst and V/TiO 2The oxygen of catalyst cuts off the result of test;
Fig. 7 shows NMO+V/TiO 2Catalyst and V/TiO 2The catalyst of catalyst reoxidizes the result of test;
Fig. 8 has shown the testing result of the nitric oxide production amount of passing through TPO (temperature programming program (TemperatureProgrammed Program)) decomposition that depends on temperature, to infer that ammonium nitrate is at NMO+V/TiO of the present invention 2Catalyst, NMO and V/TiO 2Decomposing property on the catalyst;
Fig. 9 has shown NMO+V/TiO of the present invention 2Catalyst is to removing the performance of dioxin and/or nitrogen oxide.
[specific embodiment]
Hereinafter, will provide detailed description of the present invention.
As mentioned above, catalyst (NMO+V/TiO of the present invention 2Catalyst) comprises NMO, therefore not only at high temperature but also at low temperatures the SCR of nitrogen oxide and the removal of dioxin are shown splendid activity.
NMO exists with various forms, and for example pyrolusite, psilomelane, manganite, braunite or hausmannite are as shown in table 1 below.
Table 1
Type Form Proportion Mn(％)
Pyrolusite MnO 2 4.8 63.2
Psilomelane 3.7-4.7 45-60
Manganite Mn 2O 3·H 2O 4.2-4.4 62.4
Braunite 3Mn 2O 3·MnSiO 3 4.8 62
Hausmannite Mn 3O 4 4.8 72
Manganese spar or dialogite MnCO 3 47
Rhodonite MnSiO 3 42
Bementite Hydrosilicate 31
NMO mainly exists with the form of pyrolusite and psilomelane.The NMO that uses among the present invention is soft manganese 10 ore deposits, and wherein manganese oxide is mainly by β-MnO 2Form, its physicochemical properties are shown in Table 2.
Table 2
(1) chemical analysis (weight %)
Composition ?Mn SiO 2 Al 2O 3 Fe CaO MgO O with respect to Mn and Fe 2
Weight % ?51.85 3.13 2.51 3.86 0.11 0.25 38.33
(2) physical property
Figure S2006800412255D00081
As shown in table 2, the NMO that comprises different metal oxides, Mn and Fe can be used as the catalyst of SCR, and has splendid transformation efficiency of the oxides of nitrogen under low temperature (about 150 ℃).
NMO of the present invention prepares by the following method.According to the present invention, dry and roasting NMO.Carried out 4-10 hour under the preferred 100-110 of drying steps ℃, calcination steps preferably carried out under 100-500 ℃ 3-5 hour under air atmosphere.Then, 4, compacting under the 000-6, the pressure of 000 pound/square inch (psi) forms granule through the NMO of super-dry and roasting powder, and being ground to particle mean size then is the 300-425 micron.
V/TiO of the present invention 2Catalyst loads on titanium dioxide (TiO by making vanadium 2) upward form.Titania support of the present invention should be used for load SCR catalyst.That is to say,, be used to paint or the titanium dioxide of optical catalysts is not suitable for the present invention, therefore use the titanium dioxide of producing as catalyst carrier because consider performance and reason in price.Can be used as carrier of the present invention titanium dioxide preferred physical properties as shown in the following Table 3, but the invention is not restricted to this.
In following table 3, tungsten is the co-catalyst of selecting to add in the SCR catalyst, and adding tungsten is in order to improve heat durability and anti-SO 2The property.But tungsten can appreciable impact catalyst of the present invention removes the nitrogen oxide performance.
When using tungsten, can at first make titanium dichloride load tungsten, roasting forms mixture carrier, then load vanadium, perhaps titanium dioxide while load tungsten and vanadium.In roasting process, tungsten is converted into oxide, is benchmark in the weight of titanium dioxide, and the amount of tungsten oxide is about 0-15 weight %, is preferably 5-10 weight %.
Table 3
TiO 2Amount 85-100 weight %
Granularity The 15-40 nanometer
Specific area 50-120 rice 2/ gram
The anatase amount 75-100 weight %
The tungsten oxide amount 0-10 weight %
Average pore volume 0.1-0.5 centimetre 3/ gram
The example of vanadium precursor of the present invention includes but not limited to ammonium metavanadate (NH 4VO 3), vanadium oxytrichloride (VOCl 3) etc.According to the present invention, be dissolved in distilled water and oxalic acid ((COOH) by wet dipping method use 2) in quantitative ammonium metavanadate solution prepare catalyst.Particularly, calculate the amount of vanadium according to required ratio of components with respect to titanium dioxide.Therefore, consider economic benefit, performance and SO 2Oxidation susceptibility is a benchmark in the element of carrier, and the addition of vanadium is preferably 0.5-10 weight %.The vanadium precursor is dissolved in the distilled water that is heated to 50-70 ℃ with amount of calculation.In this case, when ammonium metavanadate is used as precursor, because the solubility of this precursor is very low, so its solubility increases by this way, this aqueous solution is mixed continuously with oxalic acid, slowly stirring simultaneously and obtaining pH is 2.5.The color of gained solution is a light orange.Then, this solution is mixed with the titanium dioxide of amount of calculation, continuous stirring is mixed the mixture paste that obtains so fully simultaneously, removes then and anhydrates.
According to the present invention, in order to prepare catalyst, this slurry was stirred 1 hour or the longer time, use rotation vacuum evaporation instrument at 70 ℃ of evaporation waters then.Then, the product of gained further 100-110 ℃ of drying 24 hours, is heated to 300-500 ℃ with 5-20 ℃/minute speed, under air atmosphere,, obtains catalyst this temperature roasting 1-10 hour.Drying oven of Shi Yonging and roaster do not limit its form especially in the present invention, can comprise commercially available instrument.
Then, with the NMO and the V/TiO that prepare like this 2Mix with predetermined weight ratio, use the distilled water wet mixing, wherein NMO is with amount and the V/TiO of 5-30 weight % 2Mix.In the present invention, use ball grinding method to realize high dispersive, but the invention is not restricted to this.When the amount of NMO during less than 5 weight %, the raising of removing the nitrogen oxide performance at low temperatures becomes not obvious.On the other hand, when the amount of NMO surpassed 30 weight %, the performance of removing nitrogen oxide more or less reduced.With the catalyst that mixes temperature drying 2-24 hour at 80-110 ℃, then under air atmosphere at 100-500 ℃ of roasting 2-6 hour.In this case, in the catalyst that mixes, at NMO and V/TiO 2Between chemical reaction takes place, therefore obtain and the surperficial different chemical constitution of catalyst before mixing, thereby in wide temperature range, show denitrogenation character.When handling NMO and WTiO by wet mixing 2Be mixed into high degree of dispersion, drying, then during roasting at high temperature, the high thermal energy that provides in roasting process lures that mobility of lattice oxygen arrives NMO and V/TiO into 2Between contact-making surface on, make the different structures of two kinds of catalyst reformulate novel rock-steady structures.That is to say, by MnO 2The NMO that forms and by V 2O 5And TiO 2The V/TiO that forms 2In, round the number of the Lattice Oxygen atom of metallic atom with the different oxidation numbers of each metallic atom difference.Difference in high-temperature calcination process between the oxygen affinity of metal oxide causes mobility of lattice oxygen.The structure of the mixed catalyst of gained is different from the original structure of catalyst.Therefore, NMO+V/TiO of the present invention 2Catalyst is not simple mixture, but a kind of catalyst with novel structure.
Zhi Bei catalyst of the present invention can be used in the following manner like this: on this catalyst paint metallic plate, metallic fiber, ceramic filter or alveolate texture; perhaps in this catalyst, add a little binder, extrude with the form of particle or monoblock (monolith) then.Like this, catalyst is ground to granularity equably is about the 1-10 micron to apply or to extrude this catalyst, this applying with expressing technique is well known in the art.In addition, mixed catalyst of the present invention can be used in the following manner: on this catalyst paint air preheater, perhaps on all pipes, pipeline and/or the wall of paint boiler.
The method of using catalyst of the present invention to remove nitrogen oxide is 150-450 ℃, preferred 200-400 ℃ in temperature, and GHSV is about 1000-60000 hour -1, preferred 5000-15000 hour -1With carry out under the condition that has catalyst of the present invention.
In this case, for the SCR of nitrogen oxide, preferably with the NH of 0.6-1.2 3/ NO xMol ratio provides the ammonia reducing agent.If this mol ratio less than 0.6, then causes nitrogen oxide to remove decrease in efficiency owing to lack reducing agent.On the other hand, if this mol ratio surpasses 1.2, then may give off unreacted ammonia.Especially from the waste gas that contains oxysulfide (for example sulfur dioxide), removing in the situation of nitrogen oxide, should farthest reduce the discharging of unreacted ammonia, thereby preventing from effectively to make catalyst poisoning owing to generating ammonium sulfate.
NMO+V/TiO of the present invention 2Catalyst is not only at high temperature but also also show high nitrogen oxide at low temperature to remove the reason of efficient be because prevented the oxidation of ammonia, and by the surface texture of catalyst that mixed two kinds of substance changes, thereby shown cooperative effect.When NMO is used alone as the SCR catalyst for reaction, can make the ammoxidation that adds as reducing agent by the high oxidative capacity of NMO under 300 ℃ high temperature.Like this, the oxidation of ammonia generates NO or NO 2, these products are preferably removed by reduction.In addition, show reduction although ammonia is attracted to catalyst surface, because the amount of oxidation ammonia is not enough, so the SCR reaction can not further be carried out.As a result, the removal efficient of nitrogen oxide may descend.Therefore, NMO can only just can be used alone as the SCR catalyst in being equal to or less than 200 ℃ temperature range.That is to say that in the wide temperature range that comprises low temperature below 250 ℃ or 250 ℃ and the high temperature more than 300 ℃ or 300 ℃, the NMO with high oxidative capacity can't be used as the SCR catalyst.
Therefore, as in the present invention, when passing through to mix NMO and V/TiO 2During the preparation catalyst, can overcome the problems referred to above.That is to say, by using V/TiO 2Catalyst can prevent the ammoxidation of NMO under the high temperature, and ammonia strengthens as the availability of reducing agent like this.Like this, the inventor thinks that catalyst of the present invention is not only at high temperature but also at low temperatures also than conventional V/TiO 2The reason that catalyst has a higher activity be because by with the NMO Compositing Change performance of catalyst.In order to estimate the performance of catalyst of the present invention, carry out oxygen and cut off test.SCR reaction is a kind of in the oxidation/reduction reaction.Oxidation/reduction reaction is undertaken by the transfer of electronics between catalyst and the chemical substance, and effectively electronics shifts and produces high activity.In the reaction of reality, the migration by oxygen realizes that electronics shifts.Like this, the Lattice Oxygen of catalyst is as electron acceptor or electron donor.Therefore, the Lattice Oxygen of catalyst is considered to determine the important factors of catalyst activity.The oxygen that is used for the Lattice Oxygen of evaluate catalysts cuts off test to carry out in the following manner.Promptly under predetermined temperature (200 ℃ in the present invention) with 200ppm NO, 200ppmNH 3Join each catalyst of the present invention and conventional V/TiO with 15% oxygen 2In the catalyst, in the process that the SCR stable reaction is carried out, cut off the supply of oxygen immediately,, begin oxygen supply again immediately, detect the concentration of emission of NO cutting off oxygen supply after 1 hour.When oxygen supply was cut off, the SCR reaction utilized the Lattice Oxygen of catalyst to carry out.That is to say, after the supply of cutting off oxygen, because the SCR reaction utilizes this Lattice Oxygen to carry out predetermined a period of time, so the removal efficient of nitrogen oxide does not obviously descend.As long as catalyst shows nitrogen oxide and removes efficient, illustrate that then catalyst provides Lattice Oxygen.Show nitrogen oxide and remove being directly proportional with the Lattice Oxygen quantity of catalyst during this period of time of efficient.
Denitrification catalyst of the present invention is used to show the ability that catalyst crystal lattice oxygen is provided, and that is to say, improves the oxidability and the reducing power of Lattice Oxygen.Reoxidize test by catalyst and can determine this class character.Add each catalyst of the present invention and conventional denitrification catalyst according to scheduled volume, then with 0.5%NH 3400 ℃ of reactions 30 minutes, so that its reduction, the catalyst with reduction was cooled to room temperature after this, adds 1%O then 2When oxygen signal reaches stable state, use gaseous oxygen that the catalyst of reduction is reoxidized, simultaneously with 10 ℃/minute speed heating, in this process, use QMS (Prisma TM QMI 422, Pei Fuer vacuum company (Pfeiffer Vacuum Co.), Germany) measure the amount of the oxygen that consumes.According to this test, when the required temperature of oxygen consumption was low, the character that reoxidizes of oxygen was considered to splendid.That is to say, reoxidize test, even can prove that catalyst of the present invention also has good nitrogen oxide at low temperatures and removes performance by oxygen cut-out test and catalyst.
In addition, catalyst of the present invention can decompose the ammonium nitrate that forms at low temperatures on catalyst surface.According to the present invention, 1 gram ammonium nitrate is loaded on the 10 grams catalyst of the present invention, dry then.When at flow be 50 cc/min 3% oxygen in the presence of obtain like this with 10 ℃/minute speed heating, 0.1 gram sample the time, ammonium nitrate begins to decompose at 173 ℃.
And, in waste gas, there is in the situation of dioxin NMO+V/TiO of the present invention 2Catalyst can be realized the removal of the SCR and the dioxin of nitrogen oxide simultaneously.This is different because of the avtive spot (V-O-Ti) of dioxin generation oxidation on the catalyst of the present invention avtive spot (for example V=O and V-OH) required with removing nitrogen oxide.Usually, although there is the 0-500ppm dioxin in the waste gas of incinerator, can use catalyst of the present invention to remove these dioxins.
Therefore, catalyst of the present invention can be used for not only comprising high temperature range but also comprises that (150-450 ℃) carries out the removal of the SCR and the dioxin of nitrogen oxide in the temperature range of low temperature range.Especially the ammonium nitrate that forms on catalyst surface can decompose at low temperatures, therefore can prevent the inactivation of catalyst at low temperatures.And, can reduce the discharging of unreacted ammonium, therefore prevented the poisoning certainly of catalyst and the formation of ammonium sulfate.Thereby activity of such catalysts can desirably continue.And it is favourable using catalyst of the present invention, because dioxin can remove with nitrogen oxide, thereby has reduced the cost of keeping extra dioxin disposal system, produces economic benefit.
In the present invention, the nitrogen oxide of estimating the catalyst of the present invention be used for removing nitrogen oxide and/or dioxin is removed the used fixed bed reactors of performance and is shown among Fig. 1.As shown in Figure 1, fixed bed reactors comprise air feed part, reactive moieties and active gases analysis part.Leading to gas in the reactor 10 comprises nitrogen 1, oxygen 2, nitric oxide 3 and as the ammonia 4 of reducing agent, uses the flow of mass flow controller (MFC) 6 each gas of control of air feed steel cylinder.In addition, supply water in such a way, make nitrogen add in the reactor to be included in the state that passes through the aqueous solution in the water simultaneously.Like this, use the thermostat of double jacket type bubbler 7 outsides that the water of predetermined temperature is circulated, so that the supply of water is even.Air supply pipe in the reactor is preferably made by stainless steel.Reactive moieties is continuous flow pattern fixed-bed reactor, is 8 millimeters, highly is that 60 centimetres quartz ampoule 11 is made by internal diameter, and comprise the mineral wool that is used for fixing catalyst bed 12.Use is installed in the temperature of the thermocouple on fixed bed top by temperature controller 9 conditioned reaction devices.And, by having the air feed part is measured in bottom that identical shaped thermocouple is installed in catalyst layer with the temperature difference between the upper and lower of determining catalyst bed temperature.
For the concentration of analytical reactions thing and product, use on-dispersive (dispersion) type infrared gas analyser 14 to measure nitric oxide.Like this, before leading to gas analyzer, use dehydrater 13 to remove earlier and anhydrate.
In addition, remove performance, device that can design of graphics 1 in order to estimate dioxin.That is to say that in nitrogen 1 ' lead to air feed part, by having 1 of predetermined concentration, the aqueous solution 8 of 2-DCB (dichloro-benzenes) makes up reactive moieties under condition same as described above simultaneously.In the test section, use total hydrocarbon (THC) detector 15 to measure 1, the concentration of emission of 2-DCB.In this case, 1, the structure of 2-DCB is similar to dioxin, therefore is widely used as being used for the material that dioxin decomposes.
The nitrogen oxide that uses device shown in Figure 1 to carry out denitrification catalyst of the present invention is removed performance test.In order to keep the uniformity of denitrification catalyst, use hydraulic press under the pressure of 5000psi, the catalyst of preparation to be pressed into granule, filter then, obtaining granularity is 40-50 purpose catalyst.Use the catalyst of controlled in size, carry out the denitrogenation test with stable state according to following steps.
1) catalyst with scheduled volume is loaded in the reactor 11.
2) with catalyst under air atmosphere 400 ℃ of preliminary treatment 1 hour, to remove the impurity in the catalyst, obtain uniform oxidation state.
3) will be cooled to required probe temperature through preprocessed catalyst, keep 1 hour, reach the stable state of probe temperature in this temperature.
4) when probe temperature reaches stable state, the known gas of scheduled volume is fed in the reactor, carry out reaction test, remain unchanged up to the concentration of product, write down concentration then.
The amino-oxide of denitrification catalyst is removed performance and is represented that with transformation efficiency of the oxides of nitrogen the following formula 1 of foundation calculates:
Formula 1
Figure S2006800412255D00141
By controlling 1, the feed consistency of 2-DCB uses device shown in Figure 1 to carry out NMO+V/TiO of the present invention 21 of catalyst, 2-DCB removes performance test.In addition, the dioxin of catalyst of the present invention is removed performance with 1, and the 2-DCB conversion ratio is represented, calculates according to following formula 2:
Formula 2
Figure S2006800412255D00142
Embodiment of the present invention
The present invention may be better understood by following illustrative embodiment, but these embodiment should not be construed as restriction the present invention.
Preparation embodiment 1
Preparation NMO
Do not carrying out under any other chemically treated situation, with NMO 100-110 ℃ dry 4-12 hour down, then under air atmosphere 400 ℃ of roastings 4 hours.To be pressed into granule under the pressure of the NMO of super-dry and roasting powder at 5000psi, being ground to particle mean size then is 400 microns.
Preparation embodiment 2
Prepare the not V/TiO of tungstenic 2(N)
The metavanadic acid ammonia of 2 weight % is quantitative with respect to the titania support that 100 grams have character shown in the table 3, be dissolved in then in 150 ml distilled waters that are heated to 60 ℃.In this case,, add oxalic acid, make the pH value of solution reach 2.5 in order to improve the solubility of ammonium metavanadate.This solution is mixed with titania support, fully stir, make slurries.Then, use rotation vacuum evaporation instrument to dewater at 70 ℃.The product of gained further 110 ℃ of dryings 24 hours, carries out rough lapping then.To install in the tubular type roaster through the catalyst fines that grinds, under situation, be heated 400 ℃ with 10 ℃/minute speed with 500 ml/min flow bubbling airs, then under air atmosphere this temperature roasting 4 hours.Hereinafter, the V/TiO of not load tungsten on it 2Catalyst is called V/TiO 2(N).
Preparation embodiment 3
The V/TiO of preparation tungstenic 2(W)
With 12.35 gram ammonium tungstate ((NH 4) 2WO 4) be dissolved in 30 ml distilled waters, with gained solution be heated to about 60 ℃ so that ammonium tungstate dissolve fully.Behind the solution cool to room temperature,, obtain slurries to wherein adding 100 gram titanium dioxide.These slurries are heated to about 70 ℃, stir simultaneously, so that water evaporates from slurries.After water evaporation is finished, 120 ℃ of dryings 24 hours, then under air atmosphere 500 ℃ of roastings 10 hours, make tungsten-titanium dioxide mixed carrier like this.Then, carry out with preparation embodiment 2 in identical step, obtain the V/TiO of load tungsten on it 2Catalyst, it is called V/TiO 2(W).
Embodiment 1
To prepare the NMO of embodiment 1 and the V/TiO of preparation embodiment 2 by ball-milling technology 2(N) catalyst mix makes mixed catalyst like this.With V/TiO 2(N) catalyst mixes with 10: 1 weight ratio with NMO, carries out ball milling then.
Embodiment 2
Prepare mixed catalyst according to the method identical, different NMO that is to use preparation embodiment 1 and the V/TiO of preparation embodiment 3 with embodiment 1 2(W) catalyst.
Embodiment 3
Nitrogen oxide is removed performance
Under low temperature and high temperature, use the fixed bed testing arrangement of Fig. 1, to the catalyst (NMO+V/TiO of embodiment 1 2(N)), the catalyst (NMO+V/TiO of embodiment 2 2(W)), as with the catalyst (NMO) of catalyst of the present invention preparation embodiment 1 relatively, the catalyst (V/TiO of preparation embodiment 2 2(N)), the catalyst (V/TiO of preparation embodiment 3 2(W)) carry out the test that nitrogen oxide is removed performance.Then, provide 200ppm NO x, 15% oxygen and 8% water, supply nitrogen and make that total gas couette is 500 ml/min.Load 0.5 milliliter of denitrification catalyst, GHSV was set in 60000 hours -1Reducing agent comprises urea or ammonia, uses ammonia as reducing agent in the present embodiment.NH 3/ NO xMol ratio be 1.0, reaction temperature is adjusted to 150-300 ℃.Measure nitrogen oxide and remove the concentration of emission of performance and unreacted ammonia.The results are shown among following table 4, Fig. 2 and Fig. 3.
Remove in the test result of performance at nitrogen oxide,, can find out NMO+V/TiO in the wide temperature range that comprises low temperature and high temperature as table 4 and shown in Figure 2 2(N) catalyst is than NMO or V/TiO 2(N) catalyst has higher activity.Like this, NMO has splendid nitrogen oxide removal performance, V/TiO at low temperatures 2(N) catalyst at high temperature has splendid nitrogen oxide removal performance.In addition, by mixing the NMO+V/TiO that above-mentioned catalyst obtains 2(N) nitrogen oxide of catalyst is removed the relevant single activity of such catalysts height of specific activity, and the inventor thinks that this is because by mixing NMO and V/TiO 2Form Mn-V-TiO 2The cooperative effect of combined oxidation deposits yields has improved SCR, thereby has obviously strengthened the activity that catalyst is removed nitrogen oxide.
Table 4
Figure S2006800412255D00171
Fig. 3 and table 4 have shown the result who removes the concentration of emission of the unreacted ammonia that obtains simultaneously in the performance test at nitrogen oxide.Can find out obviously that from the result of table 4 and Fig. 3 the concentration of emission of unreacted ammonia and nitrogen oxide are removed efficient and be inversely proportional to.Especially confirmed to use NMO+V/TiO 2(N) concentration of emission of unreacted ammonia is lower than use NMO or V/TiO the time 2(N) concentration of emission of unreacted ammonia during catalyst.Therefore, verified mixed catalyst of the present invention can reduce the discharging of unreacted ammonia.
In addition, use V/TiO 2(W) catalyst is measured the concentration of emission that nitrogen oxide is removed performance and unreacted ammonia as mentioned above.The results are shown in table 5, the Figure 4 and 5.The result of Fig. 4 is similar to the result of Fig. 2.Although owing to exist tungsten to make V/TiO 2(W) low temperature active of catalyst is higher than V/TiO 2(N) low temperature active of catalyst, but this low temperature active is similar to the low temperature active of the catalyst of the present invention that comprises NMO.Certainly, compare with independent use NMO, the catalyst of the present invention that comprises NMO has better low temperature and high temperature active.Therefore, no matter whether titania support comprises tungsten, adds the nitrogen oxide removal performance that NMO can improve catalyst.Fig. 5 has shown the concentration of emission of unreacted ammonia, and this result is similar to the result of Fig. 3.
In the situation of NMO, in being equal to or higher than 250 ℃ high temperature range, nitrogen oxide is removed performance and is descended, but does not detect unreacted ammonia.This means that the ammonia that adds as reducing agent is oxidized, therefore not too be suitable as reducing agent.Because ammonia oxidation meeting at high temperature causes forming NO or NO 2So, also need the ammonia reducing agent.At high temperature, the oxidizing property of NMO has reduced nitrogen oxide removal performance.But, as described in the present invention, can be by mixing NMO and V/TiO 2Catalyst overcomes the problems referred to above.From NMO+V/TiO 2(W) evaluation result of catalyst activity can confirm, at high temperature can obtain the low emission that high nitrogen oxide is removed efficient and unreacted ammonia.And, as at NMO+V/TiO 2(N) viewed in the catalyst, as NMO and V/TiO 2During catalyst mix, prevented the oxidation of ammonia.Therefore, provide a kind of cooperative effect, removed efficient even in the high-temperature scope, also can show high nitrogen oxide.
Table 5
Figure S2006800412255D00181
Embodiment 4
Nitrogen oxide is removed the dependence of performance to the NMO mixing ratio
According to NMO+V/TiO 2The ratio of NMO is estimated nitrogen oxide and is removed performance in the catalyst.The results are shown in the following table 6.As shown in table 6, be equal to or less than under 250 ℃ the low temperature, when the consumption of NMO was 5-30 weight %, nitrogen oxide was removed efficient and is improved.But, when the consumption of NMO reaches 40 weight % above 30 weight %, remove efficient and descend on the contrary.Therefore, the consumption of preferred NMO is about 5-30 weight %.
Table 6
Figure S2006800412255D00191
Embodiment 5
Oxygen cuts off test
In order to estimate NMO+V/TiO of the present invention 2Catalyst and conventional V/TiO 2The ability that Lattice Oxygen is provided of catalyst is carried out oxygen and is cut off test.The results are shown among Fig. 6.After the oxygen supply was cut off, nitrogen oxide was removed efficient and is sharply descended immediately.But nitrogen oxide is removed efficient and can not descended always, but keeps one section preset time, and then descends.The inventor thinks that this is to carry out because SCR is reflected under the situation of Lattice Oxygen of spent catalyst.
As shown in Figure 6, because Lattice Oxygen very capable of catalyst, NMO+V/TiO are provided 2Catalyst keeps its active time ratio V/TiO 2Catalyst is long.Therefore, can more effectively carry out SCR by oxidation and/or the reduction of using Lattice Oxygen.Above-mentioned test is carried out under 200 ℃ low temperature.When high temperature, there is not special difference between this ability of two kinds of catalyst.Therefore, the nitrogen oxide of catalyst of the present invention is removed efficient why higher reason is it and provides the ability of Lattice Oxygen very good at low temperatures.
Embodiment 6
Catalyst reoxidizes test
In order to estimate NMO+V/TiO of the present invention 2Catalyst and conventional V/TiO 2The oxidability of catalyst reoxidizes test.The results are shown among Fig. 7.This test is carried out by this way, and promptly the catalyst to reduction provides oxygen, measures the required temperature of oxygen consumed in the process that temperature raises.At conventional V/TiO 2In the catalyst, oxygen is in about 335 ℃ of consumption, and NMO+V/TiO of the present invention 2Catalyst is in about 325 ℃ of oxygen consumed, and the temperature when this temperature ratio uses conventional catalyst is hanged down 10 ℃ approximately.Therefore, catalyst of the present invention has the ability that Lattice Oxygen is provided described in the splendid embodiment 5, but also has because the height of gaseous oxygen reoxidizes ability, therefore has better oxidation and/or reducing power than conventional catalyst.At last, by above-mentioned test, catalyst of the present invention is proved not only at high temperature but also all has a higher activity under low temperature.
In addition, it should be noted that NMO+V/TiO of the present invention 2Catalyst is not simple catalyst mixture.If two kinds of materials simply mix, expect that then reoxidizing of oxygen acts on NMO and V/TiO 2The specific region in take place.That is to say, if NMO+V/TiO 2Catalyst is a simple mixtures, although oxygen is not observed this phenomenon in about 335 ℃ of consumption in Fig. 7.This means NMO+V/TiO of the present invention 2Catalyst is a kind of noval chemical compound, and wherein each component substances is by chemical reaction combination again.That is to say, by with NMO and V/TiO 2Wet mixing, drying, roasting then cause on the surface of two kinds of materials chemical reaction taking place, and the result forms new construction and the catalyst of the present invention that makes can not be thought the simple mixtures of two kinds of materials, but a kind of catalyst material of novelty.
Embodiment 7
The ammonium nitrate decomposability
Be deposited on the decomposition of the ammonium nitrate on the catalyst and cause the required temperature of this decomposition and may directly influence SCR activity of such catalysts and durability in the low temperature range.Therefore, catalyst needs salt thereon to decompose in essence.Therefore, the ammonium nitrate by catalyst of the present invention decomposes the anti-middle toxicity of test evaluation.
In order to measure the decomposition temperature that can in low temperature range, make the ammonium nitrate of catalysqt deactivation, 1 gram ammonium nitrate artificial workload is restrained NMO+V/TiO of the present invention 10 2On the catalyst, dry then.Do not changing the desorb peak, when the flow with 50 ml/min provides 110 ℃ 3% oxygen, 0.1 gram catalyst is being heated to 300 ℃, observing the decomposition situation of ammonium nitrate with 10 ℃/minute speed.The results are shown among Fig. 8.
As shown in Figure 8, at about 173 ℃, ammonium nitrate is at NMO+V/TiO 2Begin under the effect of catalyst to decompose.Therefore, can be equal to or less than under 180 ℃ the low operating temperature, use mixed catalyst of the present invention to decompose ammonium nitrate, thereby prevent catalyst poisoning, the result suppresses the inactivation of catalyst under the low temperature, and guarantees the activity of such catalysts site.
Embodiment 8
Dioxin is removed performance
In order to estimate the performance of using catalyst of the present invention to remove the dioxin that contains in the waste gas, use 1,2-DCB (dichloro-benzenes), the structure of this material and dioxins seemingly can be with acting on the material that dioxin decomposes.Carry out three tests, comprise 3 described identical SCR tests (SCR test), cause nitrogen oxide and 1, the test (test of SCR+ dioxin) that 2-DCB removes by feeding in raw material simultaneously with embodiment, with by only adding 1,2-DCB estimates the test (dioxin test) of decomposability.
At GHSV is 10000 hours -1Situation under, use 800ppmNO x, 3% oxygen, NH 3/ NO xBe 1.0 and a certain amount of catalyst carry out SCR test.The test of SCR+ dioxin is identical with the SCR test, and different is to add 300ppm 1,2-DCB.Only use 300ppm 1,2-DCB and 3% oxygen carry out the dioxin test.Like this, GHSV is set in 10000 hours -1
Nitrogen oxide when Fig. 9 has shown SCR test and the test of SCR+ dioxin is removed performance.In addition, when test of SCR+ dioxin and dioxin test, describe 1 together, the removal performance of 2-DCB.As shown in Figure 9, even use 1,2-DCB, it is also as broad as long that nitrogen oxide is removed performance.In addition,, SCR carries out together even reacting, and 1, the removal performance of 2-DCB does not almost have difference yet.This is that the avtive spot of 2-DCB is V-O-Ti, is V=O and V-OH and be used for SCR reactive activity site because the vanadium/titania catalyst is used for oxidation 1.In addition, under given condition, 1, the removal efficient of 2-DCB is equal to or higher than 90%.Therefore, when using mixed catalyst of the present invention, the dioxin in the waste gas can not influence nitrogen oxide and remove reaction, and can be removed when SCR reacts.
Industrial applicability
As mentioned above, the invention provides a kind of pass through to mix NMO and V/TiO 2The catalyst of denitrification catalyst preparation, and the method for using this catalyst.According to the present invention, remove the NMO of performance and at high temperature have the active V/TiO of high nitrogen oxide removal having high nitrogen oxide at low temperatures 2A kind of raw catelyst that catalyst mix, the activity of be removed like this nitrogen oxide and dioxin are higher than these catalyst when using separately.Therefore, catalyst of the present invention not only can be used for during high temperature that conventional denitrogenation system has been suitable for uses, but also in the low temperature range that can not use applicable to conventional denitrification catalyst.
In the waste gas disposal process of routine, because lower in the temperature of dust arrester and/or desulphurization system back waste gas, conventional denitrification catalyst can't use.But, NMO+V/TiO of the present invention 2Even catalyst also can be operated being equal to or less than under 250 ℃ the low temperature, therefore can be used in the conventional waste gas disposal system.In addition, when conventional denitrification catalyst is used in the back of wet desulphurization system, need again heating process to form hot conditions.But when using catalyst of the present invention, this catalyst also shows the performance that is equal to or higher than conventional catalyst under the temperature that is lower than temperature commonly used.Thereby the energy that is used for again heating process reduces.
That is to say, when using NMO+V/TiO of the present invention 2The SCR system applies of catalyst is when conventional waste gas method of disposal, and the Application of Catalyst position is not too restricted, therefore can effectively utilize the space.Therefore, cost descends under the situation that does not need new system.In addition, because at low temperatures active higher of catalyst of the present invention, so consumption can be less, the result has reduced the cost of system, has reduced the pressure loss of catalyst bed.
Usually, because the activity of NMO descends in high temperature range, so in high temperature range, need high temperature catalyst.In addition, in the operation of the system of discharging nitrogen oxide and dioxin, stopping of operational change and operation taken place being lower than under the temperature of stable state.Therefore, use high temperature catalyst to cause the removal efficient of nitrogen oxide and dioxin obviously to descend.But, use catalyst of the present invention can overcome the problems referred to above.
According to reaction 1, provide nitric oxide and as the ammonia of reducing agent with 1: 1 mol ratio.When providing nitric oxide and ammonia with this stoichiometric proportion, nitrogen oxide is not removed fully but discharging is arranged, and shows that unreacted ammonia is with identical ratio discharging.In addition, unreacted ammonia itself is poisonous, forms ammonium sulfate according to reaction 6 and 7.At last, the inhibition of unreacted ammonium is considered to extremely important, because it directly influences life of catalyst and activity.As mentioned above, compare NMO+V/TiO of the present invention with conventional denitrification catalyst 2Even catalyst also has high activity at low temperatures, therefore can be used for further reducing the discharging of nitrogen oxide and unreacted ammonia, thereby prevent the formation of ammonium sulfate.Usually, in order to reduce the amount of unreacted ammonia, when practical operation, provide ammonia with ratio with respect to nitrogen oxide 0.5-0.8.Especially at low temperatures, the addition along with ammonia reduces the removal efficient reduction of nitrogen oxide.Therefore, should consider the ratio adding ammonia of the discharging of unreacted ammonia with the best.Therefore, NMO+V/TiO of the present invention 2Catalyst has high activity at low temperatures, has therefore farthest increased the amount of ammonia, removes performance thereby show high nitrogen oxide.
NMO+V/TiO of the present invention 2Therefore the ammonium nitrate that catalyst can form on decomposition catalyst surface under the low temperature can prevent the inactivation of catalyst at low temperatures.
And, NMO+V/TiO 2Catalyst can be used for removing the dioxin and the nitrogen oxide that contain in the waste gas owing to have higher low temperature active.That is to say, can remove nitrogen oxide and dioxin simultaneously, because be reflected at the avtive spot that is used to remove dioxin rather than carry out at the avtive spot that is used to remove nitrogen oxide.Therefore, do not need extra dioxin disposal plant, thereby reduced installation cost.
Although for the purpose of illustrating, provided preferred implementation of the present invention, one of ordinary skill in the art would recognize that under the situation that does not depart from the scope and spirit of the present invention that disclose in the appended claims, can carry out various modifications, interpolation and alternative.

Claims (9)

1. a vanadium/titania is catalyst based, this catalyst comprises the natural manganese ore that is used for removing nitrogen oxide and dioxin in wide operating temperature range, wherein, be applicable to the natural manganese ore of the catalyst based 5-30 of the comprising weight of vanadium/titania % of removal of dioxin contained in the SCR of nitrogen oxide contained in the waste gas and the waste gas and the vanadium of 0.5-10 weight %.
2. vanadium/titania as claimed in claim 1 is catalyst based, it is characterized in that, this catalyst also comprises the tungsten oxide of 0-15 weight %, is benchmark in the weight of titanium dioxide.
3. vanadium/titania as claimed in claim 1 is catalyst based, it is characterized in that, the precursor of described vanadium is ammonium metavanadate or vanadium chloride.
4. vanadium/titania as claimed in claim 1 is catalyst based, it is characterized in that, described natural manganese ore is by β-MnO 2The pyrolusite of forming.
5. catalyst based as each the described vanadium/titania among the claim 1-4, it is characterized in that by add a little binder in described catalyst, described catalyst is extruded with the form of particle or monoblock.
6. each described vanadium/titania is catalyst based in the claim 1 to 4, it is characterized in that, described catalyst is applied on the structure that is selected from down group: metallic plate, metallic fiber, ceramic filter and alveolate texture.
7. catalyst based as each described vanadium/titania in the claim 1 to 4, it is characterized in that described catalyst is applied on pipe group, pipeline and/or the wall of air preheater or boiler.
8. optionally contained nitrogen oxide and the method for removing dioxin contained in the waste gas in the catalytic reduction waste gas, this method are that 150-450 ℃, gas hourly space velocity are 1000-60000 hour in temperature -1With carry out under the condition that has each catalyst in the claim 1 to 4.
9. method as claimed in claim 8 is characterized in that, when the SCR of nitrogen oxide, with the NH of 0.6-1.2 3/ NO xMol ratio provides the ammonia as reducing agent.
CN2006800412255A 2005-09-27 2006-08-31 Vanadium/titania catalyst comprising natural manganese ore for removing nitrogen oxides and dioxin in wide operating temperature range and method of using the same Expired - Fee Related CN101300068B (en)

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